4 Functional Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.1 Elastin-Like Polypeptides and Drug Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.2 Columnar Stacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
4.3 Pi-Conjugated Macromolecules for Organic Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
1 Introduction
To state that precise knowledge of the structure and dynamics of macromolecules of
well-defined architectures is of utmost importance when tailoring them for specific
functions nowadays sounds like ululas Athenas portare. In his Nobel lecture in 1953
on macromolecular chemistry [1] Hermann Staudinger emphasized the importance of
determining the structure of macromolecules, but did not mention their dynamics. He
listed several experimental techniques for determining the structure and the molecular weight of macromolecules that were in use at that time, when the macromolecular nature of both synthetic and biomacromolecules was under debate, but magnetic
resonance was not among them. This is easily explained by the fact that magnetic
resonance (MR) techniques based on electron spins (i.e., electron paramagnetic
resonance, EPR, spectroscopy) and on nuclear spins (i.e., nuclear magnetic resonance, NMR, spectroscopy) were in their infancies, being discovered in 1944 by
E. K. Zavoisky [2], and in 1945 by F. Bloch and E.M. Purcell, respectively
[3, 4]. Naturally, their potential in macromolecular science was not yet known. As
early as the 1960s, however, G. Natta and coworkers took advantage of the new NMR
technique to elucidate the stereoregularity of poly(propylene) [5], providing a new
way of structural characterization of macromolecular chains [6]. Polymer dynamics
is closely linked to the mechanical properties of polymer materials [7]. As molecular
dynamics leads to narrowing of NMR lines, the analysis of
1
H NMR line shapes of
bulk polymers offered a means for a better understanding of these delicate relationships [8]. Indeed, as early as 1959, W. P. Slichter published a seminal paper [9], again
in Staudinger’s journal, entitled “Nuclear resonance studies of motion in polymers,”
describing these developments. Much later,
2
H NMR on selectively deuterated polymers provided unique possibilities for elucidating both the time scale and geometry of
molecular dynamics in polymers [10].
Today, NMR spectroscopy has advanced to become an indispensable tool in
polymer research. The introduction of Fourier transform NMR and its extension to
two and higher dimensions [11] made it possible to include low-sensitivity, yet highly
informative, spectroscopy of rare nuclei such as
13
C or
15
N. These techniques are now
mainly applied to study biomacromolecules [12] in solution, but increasingly also in
the solid state [13]. In the latter case, multidimensional NMR techniques were
actually developed first for synthetic polymers [14]. Later, advances in solid state
296
H.W. Spiess
4.1 Elastin-Like Polypeptides and Drug Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.2 Columnar Stacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
4.3 Pi-Conjugated Macromolecules for Organic Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
1 Introduction
To state that precise knowledge of the structure and dynamics of macromolecules of
well-defined architectures is of utmost importance when tailoring them for specific
functions nowadays sounds like ululas Athenas portare. In his Nobel lecture in 1953
on macromolecular chemistry [1] Hermann Staudinger emphasized the importance of
determining the structure of macromolecules, but did not mention their dynamics. He
listed several experimental techniques for determining the structure and the molecular weight of macromolecules that were in use at that time, when the macromolecular nature of both synthetic and biomacromolecules was under debate, but magnetic
resonance was not among them. This is easily explained by the fact that magnetic
resonance (MR) techniques based on electron spins (i.e., electron paramagnetic
resonance, EPR, spectroscopy) and on nuclear spins (i.e., nuclear magnetic resonance, NMR, spectroscopy) were in their infancies, being discovered in 1944 by
E. K. Zavoisky [2], and in 1945 by F. Bloch and E.M. Purcell, respectively
[3, 4]. Naturally, their potential in macromolecular science was not yet known. As
early as the 1960s, however, G. Natta and coworkers took advantage of the new NMR
technique to elucidate the stereoregularity of poly(propylene) [5], providing a new
way of structural characterization of macromolecular chains [6]. Polymer dynamics
is closely linked to the mechanical properties of polymer materials [7]. As molecular
dynamics leads to narrowing of NMR lines, the analysis of
1
H NMR line shapes of
bulk polymers offered a means for a better understanding of these delicate relationships [8]. Indeed, as early as 1959, W. P. Slichter published a seminal paper [9], again
in Staudinger’s journal, entitled “Nuclear resonance studies of motion in polymers,”
describing these developments. Much later,
2
H NMR on selectively deuterated polymers provided unique possibilities for elucidating both the time scale and geometry of
molecular dynamics in polymers [10].
Today, NMR spectroscopy has advanced to become an indispensable tool in
polymer research. The introduction of Fourier transform NMR and its extension to
two and higher dimensions [11] made it possible to include low-sensitivity, yet highly
informative, spectroscopy of rare nuclei such as
13
C or
15
N. These techniques are now
mainly applied to study biomacromolecules [12] in solution, but increasingly also in
the solid state [13]. In the latter case, multidimensional NMR techniques were
actually developed first for synthetic polymers [14]. Later, advances in solid state
296
H.W. Spiess